Process of making slow-setting casein glue, and dry base for use in such processes



Patented @ct. 27, 1931 l'l'ED STATES l LAWRENCE BRADSHAW AND HENRY V.DUNHAM, OF BAINBRIDGE, NEW YORK, AS- SIGNORS, BY MESNE ASSIGNMENTS, TOTHE CASEIN MANUFACTURING COMPANY OF AMERICA, INC., OF NEW YORK, N. Y., ACORPORATION OF DELAWARE PROCESS OF SLOW-SETTING CASEIN GLUE, AND DRYBASE FOR USE IN SUCH PROCESSES No Drawing.

10, of time which may elapse between the initial mixing with water andthe point at which the glue sets, i. e., becomes too thick to spread.Various methods have been proposed to con trol this interval, generallytermed the life "15 of the glue, such as the addition of animal glue orsalts of the alkali or alkaline earth metals. The use of animal glue forthis purpose' is uneconomical, since its natural strength, whichotherwise would contribute to the adhesiveness of the mixture,depreciates considerably under these conditions. The addition tocaseinglues and adhesive compositions, of alkali metal phosphates,

.fluorides and other salts which by interaction 25 with lime liberatecaustic alkalies is undesirable beyond a certain point; that is to say,

any large excess of alkali over the amountsp required to dissolve thecasein and to impart a proper consistency and ultimate water-re- 30sisting property to the glue or adhesive is to be avoided since thecaustic alkali thus produced causes hydrolysis of the casein andconsequent loss of strength.

We have now found that soybean meal added to casein glues and adhesivecompositions has a marked effect in retarding the setting thereof,thereby extending the life of such glues and adhesive compositions. Asexam les, the rates of change in the viscosity o a commercial caseinglue- (A) and of the same glue with respectively 7 (B), 15% (C) and 30%(D), of pulverized soybean meal added (in place of equivalent amounts ofthe casein) are compared below.- The values represent readings on theStormer viscosimeter (provided with a 500 gram weight)-at, regularintervals after mixing, the conditions of making the four liquid gluesA, B, C and D being identical in every respect, except as to theaddition or omis- Application filed May 19, 1926. Serial No. 110,298.

sion of the stated amounts of soybean meal.

The commercial casein glue here referred to was a mixture of dry casein,alkaline salts of sodium, sodium fiuori-de and hydrated lime, mixedtogether in proportions similar tothose described in the presentapplication. The said commercial casein glue base and each of thecomposite glue bases referred to herein were mixed in every case withdouble their weight of water at approximately 60 F., and themeasurements of the viscosities of the glues thus prepared were made ata constant temperature of 70 F.

| 1211'. Bhrs. BhrS. 7111's. Qhrs. 11 hrs. 13 hrs.

A 26 9 2 set i B 30 24 11 6 2% 2 1% C 24 17 12 7 4 3 2 D 22 14 10 9 7 66 .smoother glue is obtained.

By the term 80 mesh as used above and in certain of the claims, we meanthat the meal should be of such a degree of fineness as to pass throughan 80 mesh standard screen without leaving any substantial residue. Theparticles are not of uniform size. While the coarsest grains mayapproximate 80 mesh, it is obvious that, in the milling process, aconsiderable proportion of the particles are reduced to much smallerdimensions.

In carrying out the invention the casein is mixed with an appropriateamount of the soybean meal, and to this mixture is added an alkalineearth oxide or hydroxide with or without one or more water solublealkali metal salts, preferably those which by them- I selves reactalkaline to litmus and are capable of dissolving the casein and theproteids of the soybean meal. The salts are such as react with hydratedlime, in the resence of water, to liberate caustic alkali, ib. g.caustic soda). It is well known that caustic alkali andalkaline-reacting salts of alkali metals both are capable (in thelpresence of water) of dissolving casein, and t ey both also candissolve the proteids of the. soybean meal. The alkali metalsalts ofalkaline charpresent and the water will then serve to re- I act upon thecasein and the proteids contained in the soybean meal. Likewise onadding water to a mixture of the casein, soybean meal and lime, the limeand water will react with the said proteids.

The followin examples of mixes which have given satis actory resultswhen applied to 'ointsand laminated woods will serve to dehne moreparticularly the character of the invention, but we do not desire to belimited to the particular compounds or proportions herein set forth. Theparts are by weight.

In referring to an alkaline earth oxide or hydroxide-we include, for thesake of convenience, the oxide and hydroxide of magnesium.

Examplel Casein parts; soybean meal (120 mesh) 10 parts; hydrated lime15 parts; sodium fluoride 5 parts; sodium carbonate 5 parts; sodiumphosphate 3 parts.

Emample 2 'Casein 35 parts; soybean meal '30 parts; hydrated lime 20parts; sodium fluoride 4 parts; sodium carbonate 9 parts.

Example 3 Casein 50 parts; soybean meal 20 parts, hydrated lime 15parts; magnesium oxide 5 parts; sodium fluoride 7 parts; trisodiumphosphate 3 parts.

Ewample Casein 40 parts; soybean meal..32- parts; hydrated lime 18parts, sodium fluoride 2 parts; sodium carbonate 7 parts; sodiumarsenate 1 part.

These examples indicate the dry materials which are mixed together toform the dry" glue base. The dry mixture is to be subsequentlyincorporated with water by the is prolonged.

methods well knowh to users of casein glues. We prefer to use from 2 to2 parts of cold water to 1 part of the dr base. The water is put into akettle provi ed with an eflicient stirring device; the dry gluebase (e.g. one of the above formulas) is added slowly and mixed thoroughly forabout 20 minutes and is then ready for use.

The term casein is used herein in its usual meaning, to denotecertainphosphoproteid matter contained in milkand ski milk, such as cows milk,etc.

The soybean meal preferably used is the product obtained by grinding thecake left in the presses after expressing the major portion of the oil;it usually contains about that the further removal of oil by treatmentthe oil from the seed with suitable solvents 6, to 8% of residual oil.It will be understood (e. g. after crushing) are not precluded. The

term soybean meal is intended to cover-- such products, as distinguishedfrom soybean containing the full natural oil content.

The addition of soybean meal to casein glues, in place of the cottonseedmeal and peanut meal as described and claimed in our application underSerial Number 99,423 is preferable in cases where a light colored glueis required, as the commercial meals of cottonseed and peanutcontainnatural coloring matters which detract from the appearance of theglues in which they are used. It is understood that in such cases weprefer to use meal from the light colored varieties of soybean, such asthe Manchurian yellow, rather than the inferior blue and black varietieswhich yield darker glues.

The term alkaline earth oxide as used herein is intended to include theunhydrated as well as the hydrated oxides (hydroxides). The term a saltis intended to cover one or severalsalts.

No claim is made herein to the use of casein or to the use of soybeanmeal, alone, as the base of the adhesive, but to the jointfuse of these,whereby the life of the adhesive with casein glues, of the extracted andreprecipitated soybean proteids, along I with casein. I

We claim i 1. A dry glue base containing a quantity of casein, a smallerquantity of soybean meal and an alkaline earthoxide together with awater-soluble alkali metal salt which can re- No claim is made to theuse,

act with lime in the presence of water to form caustic alkali and aprecipitate,-the said salt and alkaline earth oxide being in amountssufficient for the reaction products and water to dissolve the caseinand the proteids of the soybean meal, such base being adapted, uponmixing with water, to form an adhesive, which adhesive will have alonger period of workable viscosity than would a similar compositionwithout the soybean meal and with-the casein correspondingly increased.

2. A new dry glue base containing casein, soybean meal and an alkalineearth oxide, the latter being in amount sufficient to react with thecasein and the proteids in said soybean meal, such base being adaptedupon mixing with water, to form an adhesive, which adhesive will have alonger period of workable viscosity than would a similar compositionwithout the soybean meal and with the casein correspondingly increased.

3. A new dry base for the manufacture of adhesive material comprising aquantity of casein, incorporated with a smaller quantity of soybean mealground to pass an 80 mesh screen, and an alkaline earth oxide capableof, and in amount sufficient for reacting with the casein and theproteids of the soybean meal, when water is added, such base beingadapted, upon mixing with water, to form an adhesive, which adhesivewill have a longer period of workable viscosity than would a similarcomposition ,without the soybean meal and with the caseincorrespondingly increased.

4. A new dry base for the manufacture of adhesive material comprisingcasein, incorporated with soybeanmeal ground to pass a 120 mesh screen,and an alkaline earth oxide capable of, and in amount sufiicient forreacting with the casein and the proteids of the soybean meal, whenwater is added, such base being adapted, upon mixing with water, to forman adhesive, which adhesive will have a longer period of workableviscosity than would a similar composition without the soybean meal andwith the casein cor-respondingly increased.

5. A new dry base for the manufacture of adhesive material comprising aquantity of casein, incorporated with a smaller quantity of soybean mealground to pass a screen finer than 120 mesh, and an alkaline earth oxidecapable of, and in amount sufiicient for reacting with the casein andthe proteids of the soybean meal, when water is added, such base beingadapted, upon mixing with water, to form an adhesive, which adhesivewill have a longer period of workable viscosity than would a similarcomposition without the soybean meal and with the casein correspondinglyincreased.

6. A new dry base for the manufacture of adhesive compositions,comprising casein incorporated with soybean meal ground to pass an meshscreen, an alkaline earth oxide and an alkali metal salt capable, in thepresence of water, of dissolving the casein and the proteids" of thesoybean meal, the total amounts of such alkaline earth oxide materialand of such alkali metal salt being sufficient,

the casein and the proteids of the soybean meal, and the amount of suchcasein being greater than the amount of such soybean meal, such basebeing adapted, upon mixing with water, to form an adhesive, whichadhesive will have a longer period of workable viscosity than would asimilar composition without the soybean meal and with the caseincorrespondingly increased.

7. A new dry base for the manufacture of adhesive compositions,comprising casein incorporated with soybean meal from which a large partat least of the oil has been removed, ground to substantially all passthrough an 80 mesh screen, and an alkali metal salt capable o.dissolving the casein and the proteids of the soybean meal, togetherwith an alkaline earth oxide, the said salt and oxide being in amounts,in conjunction with the reaction products formed, sufficient to dissolvethe casein and the proteids of the soybean meal when water is added,such base being adapted, upon mixing with water, to form an adhesive,which adhesive will have a longer period of workable vis cosity thanwould a similar composition withoutthe soybean meal and with the caseincorrespondingly increased.

8. A-I18W dry base for the manufacture of adhesive compositionscomprising a quantity of casein incorporated with a smaller quantity ofsoybean meal from which atleast a part of the oil has been removed,ground to substantially all pass through an 80 mesh screen, and analkaline alkali metal compound capable of dissolving the casein and theproteids of the soybean meal, when water is added, together with slakedlime, the said alkali metal compound and lime being in amount sufiicientto dissolve the casein and the proteids of the soybean meal, such basebeing adapted, upon mixing with water, to foran an adhesive, whichadhesive will have a longer period of workable viscosity than would asimilar composition without the soybean meal and with the caseincorrespondingly increased.

9. A dryglue base containing casein, soybean meal and an alkaline earthoxide, to-

get-her with a water-soluble alkali metal salt which can react with limein the presence of water to form caustic alkali and a precipitate, thesaid salt and alkaline earth oxide being in amounts suflicient for thereaction products and Water to dissolve the casein and the proteids ofthe soybean meal, such base being adapted, upon mixing with water, toform an adhesive.

10. A novel material in the glue art, the

same being an intimate dry mixture of casein and soybean meal, theformer being in excess of the latter.

11. A novel material in the glue art, the

same being an intimate dry mixture of casein and soybean meal, theamount of such casein being substantially greater than the amount ofprotein contained in the soybean meal.

12. The method of producing a glue of I comparatively long working lifefrom a dry glue base including casein, a water-soluble alkali metal saltwhich is alkaline to litmus, and an alkaline earth metal oxide, whichprocess comprises incorporating soybean meal in such dry glue base, andthereafter mixing this new glue base with water, the proportion of thesoybean meal used being sulficient to retard the setting of the glueproduced by said admixture with Water.

13. A dry gluebas'e containing casein, soybean meal and lime, the latterbeing in amount sufiicient to react with the casein and the proteids insaid soybean-meal. In testimony whereof we. aflix our signatures.

LAWRENCE BRADSHAW.

- HENRY v. DUNHAM.

